ES2341441T3 - ORGANOSILICIDE DERIVATIVES OF AMINO HIDROXIBENZOFENONAS AND ITS USE AS FILTERS OF UV-A RAYS IN COSMETIC PREPARATIONS. - Google Patents

Abstract

The present invention relates to organosilicone derivatives of amino hydroxybenzophenones, a process for their preparation thereof, a cosmetic compositions comprising the organosilicone derivative and the use thereof for protecting hair and/or skin from damage caused by UV-A irradiation.

Description

Organosilicon amino derivatives hydroxybenzophenones and their use as lightning filters UV-A in cosmetic preparations.

The present invention relates to derivatives Organosilicic amino hydroxybenzophenones, to a process for its preparation, to the compositions comprising these derivatives and to use of them.

The EP-A-1046391, EP-A-1133980 and WO-A-0172935 disclose amino substituted hydroxybenzophenones as blocking agents of UVA rays, EP-A-1046391, EP-A-1133980 as lightning filters Photo-stable UV in pharmaceutical preparations and Cosmetics and WO-A-0172935 for use in textiles

The organosilicon compounds that have hydroxybenzophenone substituents which act as sun block constituents are disclosed in US-A-6114561, EP-A-0478284, EP-A-0712855, EP-A-0982310, US-A-5270426, FR-A-2684551 and GB-A-1167759.

However, no prior art document previously cited discloses organosilicon derivatives of amino hydroxybenzophenones.

More particularly, the invention relates to organosilicon compounds comprising a unit of the formula I

one

where

a is 0, 1 or 2,

R1 is hydrogen, a hydrocarbon group C_ {1} -C_ {30} saturated or unsaturated or a group trimethylsilyloxy; Y

Z is an amino substituted hydroxybenzophenone of formula III

2

where R 3 and R 4 are independently hydrogen, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 3 -C 10 cycle-
alkyl or C 3 -C 10 cycloalkenyl or R 3 and R 4, together with the nitrogen atom to which they are attached, form a 5- to 6-membered ring;

X is -O- or -NR 5 - where R 5 is hydrogen, C 1 -C 20 alkyl, C 2 -C 2 Oalquenil, C 3 -C 10 cycloalkyl or C 3 -C 10 cycloalkenyl; Y

And it is an alkenylene chain or C 3 -C 12 divalent alkylene;

and, optionally, a unit of the formula II

3

where

b is 0, 1, 2, 3; Y

R2 is hydrogen, a hydrocarbon group C_ {1} -C_ {30} saturated or unsaturated or a group trimethylsilyloxy.

Suitable organosilicon compounds are polymeric materials that can be homopolymers that consist only in units of the formula I, or they can be copolymers that they contain the two units that have the general formula I or II. The units of formula I can be distributed in a manner randomized in an organosiloxane polymer, these may be the final polymer blocking units or may be located at the end of the polymer, and earrings in a polymer chain, at Same time. Organosilicon compounds may vary from liquids that flow freely to resinous solids or materials of the rubber type, highly viscous.

If a is 2 the two substituents R1 can Be identical or different. If b is 2 or 3, both two or three R2 substituents may be identical or different. If he polymer contains more than one unit of the formula I, the R 1 substituents may be identical or different from one drive to another. If the polymer contains more than one unit of the formula II, the R2 substituents may be identical or different from one unit to another.

Examples of a hydrocarbon group C 1 -C 30 saturated or unsaturated include C 1 -C 30 alkyl such as methyl, ethyl, propyl and butyl; C 2 -C 30 alkenyl such as vinyl and alil; and substituted or unsubstituted aryl such as phenyl, alkaryl and alkoxyphenyl. The hydrocarbon group is substituted or unsubstituted for example, halogen, for example, the hydrocarbon group C 1 -C 18 halogenated.

The alkyl and alkenyl can be chain linear or branched, for example, methyl, ethyl, 3-propyl, 2-propyl, 2-methyl-3-propyl, 3-butyl, 4-butyl, 4-pentil, 5-pentil, 6-hex, 2-propen-2-il, 2-propen-3-il, 3-buten-3-il, 3-buten-4-il, 4-penten-4-il, 4-penten-5-il, (3-methyl) -penta-2,4- dien-4 or 5-il, 11-dodecen-11-il.

Examples of cycloalkyl and cycloalkenyl include cyclopropyl, 2-methyl-cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, (3-methyl) -cyclopenta-2,4-dienyl and 11-cyclododecenyl.

The terms "string C 3 -C_ {l2} divalent alkylene "and" chain C 3 -C_ {l2} divalent alkenylene " mean link groups, in particular, the link groups that bind the chromophore residue that absorbs UV radiation in half silane, oligosiloxane or polysiloxane. The examples of C 3 -C l 2 alkylene include residues of saturated straight or branched chain hydrocarbons such as the 3-propylene, 2-propylene, 2-methyl-3-propylene, 3-butylene, 4-butylene, 4-pentylene, 5-pentylene, 6-hexylene, and the like. The examples of C 3 -C_ {l2} alkenylene include residues of unsaturated hydrocarbons containing at least one double bond, such as for example 2-propen-2-ileum, 2-propen-3-ileum, 3-buten-3-ileum, 3-buten-4-ileum, 4-penten-4-ileum, 4-penten-5-ileum, (3-methyl) -penta-2,4-dien-4 or 5-ileum, 11-dodecen-11-ileum, and the like Divalent alkylene or alkenylene chains They can be interrupted by one or several oxygen atoms. The examples of oxygen interrupted linkage groups are by example 2-ethyloxy-et-2-ylene, 4-butyloxy-et-2-ylene  or 3,6-dioxa-8-octylene. Particularly preferred linkers are -CH = CH- (CH2) n -, -C (CH 2) - (CH 2) n -, -CH 2 -CH 2 - (CH 2) n - and -CH (CH 3) - (CH 2) n - where n is an integer of 0 to 10.

In the organosilicon compounds of the invention the following preferences will be applied in a way independent, collective or in any combination or sub-combination:

(a) organosilicon compounds in which the number of units of formula I is limited to a maximum of 50%, more preferably from 10 to 40%, most preferably from 30 to 40% of the total number of siloxane units in the molecule;

(b) homopolymers and copolymers of liquid substantially linear organosiloxane, for example the which have a viscosity from 50-20000 m 2 / s;

(c) organosilicon compounds where in the units of formula I the following meanings apply from independently, collectively or in any combination or sub-combination:

(C1)

to is 1;

(C2)

R1 is 80% methyl, preferably 100% units of the formula I;

(C3)

Y it's 2-propylene, 3-propylene, 2-propen-2-ileum, 2-propen-3-ileum, 4-butylene or 3-buten-4-ileum, preferably 2-propen-2-ileum or 2-propen-3-ileum;

(C4)

X is -0-;

(C5)

R 3 and R 4 are ethyl,

(d) organosilicon compounds where in the units of formula II, the following meanings apply independently, collectively or in any combination or sub- combination:

(d1)

preferably at least two units of formula II are present;

(d2)

b is 2;

(d3)

R2 is 80% methyl, preferably 100% units of the formula II.

When a = 1 and b = 2 the organosilicon compound it is a diorgano-siloxane polymer substantially linear or cyclic. However, if the Diorgano-siloxane is a substantially polymer linear at least two final block units must be present, thus requiring either the presence of two units in which to It has a value of 2 or two units in which b is 3.

A diorgano-siloxane polymer Linear Preferred (hereinafter: COMPOUND) is a polymer composed of a structural unit of formula IVa and a unit structural formula IVb

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4

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s units of the formula IVc

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5

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and r units of formula IVd

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6

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where

Z is as defined above;

R 1, R 6, R 7, R 8, R 9, R 10 and R 11 independent are as defined above for R2;

B and B 'independently are a group Z or a R2 group;

r is an integer from 0 to 200; Y

s is an integer from 0 to 50, in which, at least B or B 'is Z when s is 0.

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The compounds of the invention can be prepared by hydrosilylation of an organosilicon compound in the that each unit of formula I is replaced by a unit that It has the formula VI (hereinafter: SiH derivatives).

7

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SiH derivatives are well known in the silicone industry and are commercially available. Be described, for example, in the following patents: US 3,220,972, US 3,697,474 and US 4,340,709.

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Hydrosilylation can be carried out by reacting the SiH derivative in the presence of a catalyst  transition metal, for example, platinum on stone coal or a platinum complex catalyst, such as the complex of platinum divinyl tetramethyl disiloxane with a compound of formula VII

8

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wherein R 3, R 4 and X are as defined for formula III and Y 'has the same definition that And in formula III, but it is finished well with a double or a triple bond The addition can proceed in both positions of the unsaturated carbon-carbon bond, which leads to isomeric mixtures of organosilicon products for example containing double exo links and endo.

Hydrosilylation can be performed in a appropriate reaction solvent, for example, in isopropanol or Toluene. Reagents may be present in molar amounts. approximately equal. The reaction can be executed at a high temperature, for example, in a range from 40 ° C to 150 ° C, preferably from 60 ° C to 100 ° C, for example, at about 80 ° C

The compounds of formula VII are generally known and can be prepared, for example, from according to the procedure described in EP 1,046,391 by acylation of the corresponding amino substituted phenols followed by the reaction with the respective alcohol or amine such as propinol, allyl alcohol, vinyl alcohol, prop-2-inyl amine or vinyl amine. The Exemplary amino hydroxybenzophenones that are particularly suitable for the preparation of the compounds of the invention include the prop-2-inyl ester of acid 2- (4-diethylamino-2-hydroxybenzoyl)  benzoic acid allyl ester 2- (4-diethylamino-2-hydroxybenzoyl) benzoic acid vinyl ester 2- (4-diethylamino-2-hydroxybenzoyl)  benzoic and N-prop-2-inil acid benzamide 2- (4-diethylamino-2-hydroxybenzoyl) benzoic.

The compounds of the present invention have absorption maximums in the UV-A region and are effective in absorbing ultraviolet radiation in the UV-A range (320-400 nm), which makes them particularly suitable for use in cosmetic sunscreen preparations where absorption in UV-A range is especially desirable.

Thus, the present invention also relates to the compositions comprising the new compounds organosilicon, formulated in a suitable support or substrate. Normally, the compositions of the invention are adopted to the protection of a material that is sensitive to radiation ultraviolet, in particular solar radiation, such as the skin and / or the hair and comprises a photo-protective amount Effective of an organosilicon compound of the invention.

For the preparation of protective agents against the light, especially preparations for cosmetic use and / or dermatological, such as sunscreen formulations and skin protection for all cosmetic products On days, a compound of the present invention can be incorporated into auxiliary agents, for example, a base cosmetic, which is conventionally used for these formulations. When appropriate, other protection agents against conventional UV-A and / or UV-B rays They can also be added. The combination of UV filters It can show a synergistic effect. The preparation of said agents Lightning protection is well known by the skilled person in this field. The concentration of UV filters is not review. For example, the amount of the compounds herein invention and optionally a lightning protection agent UV-A or UV-B hydrophilic and / or additional lipophilic other than the compounds described in this invention may be in the range of from 0.5 to 12% by weight of the total composition These additional protection agents are advantageously selected from the compounds mentioned to Then, without this being limiting:

Examples of protection agents against UV-B rays, that is, the substances that have the absorption maximums between about 290 and 320 nm, which enter consideration for its combination with the compounds herein invention are, for example, the following organic compounds and inorganic: acrylates such as 2-ethylhexyl 2-cyano-3,3-diphenylacrylate (octocrylene, PARSOL® 340), ethyl-2-cyano-3,3-diphenylacrylate  and the like; camphor derivatives as 4-methyl-benzylidene camphor (PARSOL® 5000), 3-Benzylidene Camphor, Metosulfate benzalkonium camphor, polyacrylamidomethyl benzylidene camphor, sulfobenzylidene camphor, sulfomethyl benzylidene camphor, acid dialcane sulfonic terephthalidene and the like; derivatives of cinnamate as octyl methoxycinnamate (PARSOL® MCX), ethoxyethyl methoxycinnamate, diethanolamine methoxycinnamate (PARSOL® Hydro), isoamyl methoxycinnamate and the like, as well as acid derivatives cinnamic attached to siloxanes; acid derivatives p-aminobenzoic acid, such as acid p-aminobenzoic acid, 2-ethylhexyl p-dimethylaminobenzoate, ethyl p-aminobenzoate N-oxypropylene state, glyceryl p-amino benzoate; benzophenones such as benzophenone-3, benzophenone-4, 2,2 ', 4,4'-tetra-hydroxy-benzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone and the like; esters of benzalmalonic acid as di (2-ethylhexyl) 4-methoxybenzalmalonate; acid esters 2- (4-ethoxy anilinomethylene) propanedioic such as the diethyl ester of 2- (4-ethoxy acid) anilinomethylene) propanedioic as described in EP 895,776; organosiloxane compounds containing groups benzmalonate as described in EP 358,584, EP 538,431 and EP 709,080; drometrizol trisiloxane (MEXORYL XL); pigments like TiO2 microparticulates, and the like, where the term "microparticulate" refers to a particle size from around 5 nm to about 200 nm, in particular from around 15 nm to about 100 nm, and the particles of TiO2 can be coated by metal oxides such as, by example, aluminum or zirconium oxides or coatings organic, such as, for example, polyols, methicone, stearate aluminum, alkyl silane; imidazole derivatives, such as 2-phenyl benzimidazole sulfonic acid and its salts (PARSOL® HS). The salts of 2-phenyl acid Sulfonic benzimidazole are for example alkaline salts, such as sodium or potassium salts, ammonium salts, morpholine salts, salts of primary amines, sec. and third. how do you get out of monoethanolamine, diethanolamine and the like, salicylate derivatives as iso-propylbenzyl salicylate, salicylate benzyl, butyl salicylate, octyl salicylate (NEO HELIOPAN OS), isooctyl salicylate or homomentile salicylate (homosalate, HELIOPAN) and the like; triazine derivatives such as octyl triazone (UVINUL T-150), dioctyl butamido triazone (UVASORB HEB), bis ethoxyphenol methoxyphenyl triazine (TINOSORB S) and the like; a polysiloxane containing a UV-B chromophore as for example Polysilicone 15 (Dimethicodiethyl-benzalmalonate or Parsol SLX).

Examples of protection agents against UV-A rays i.e. substances that have absorption maximums between about 320 and 400 nm, which enter consideration for its combination with the compounds herein invention are, for example, the following organic compounds and inorganic: dibenzoylmethane derivatives such as 4-tert. butyl-4'-methoxy dibenzoyl methane (PARASOL® 1789), dimethoxydibenzoylmethane, isopropyldibenzoylmethane and the like; benzotriazole derivatives as 2,2'-methylene-bis- (6- (2H-benzotriazol-2-yl) -4- (1,1,3,3, -tetramethylbutyl) -phenol  (TINOSORB M) and the like; acids phenylene-1,4-bis-benzimidazole sulfonic acids or salts such as 2,2- (1,4-phenylene) acid bis- (1 H -benzimidazol-4,6-disulfonic acid)  (NEOHELIOPAN AP); amino substituted hydroxybenzophenones such as the acid hexyl ester 2- (4-diethylamino-2-hydroxy-benzoyl) -benzoic acid as described in EP 1,046,391; pigments like ZnO microparticulate and the like where the term "microparticulate" refers to a particle size from around 5 nm to about 200 nm, in particular from around 15 nm to about 100 nm, and the ZnO particles they can be coated by metal oxides such as aluminum or zirconium oxides or organic coatings, such as polyols, methicone, aluminum stearate, alkyl silane

How dibenzoylmethane derivatives have limited photo-stability may be desirable photo-stabilize these protective agents against UV-A rays Thus, the term "agent of protection against conventional UV-A rays " also refers to dibenzoylmethane derivatives as per example PARSOL® 1789 stabilized, for example, by derivatives of 3,3-diphenylacrylate as described in EP 514,491 and EP 780,119; camphor benzylidene derivatives as described in US 5,605,680; organosiloxanes containing groups benzmalonate as described in EP 358,584, EP 538,431 and EP 709,080.

The compositions of the invention can also contain usual cosmetic adjuvants and additives, such as preservatives / antioxidants, fatty substances / oils, water, organic solvents, silicones, thickeners, softeners, emulsifiers, additional sunscreens, agents defoamers, moisturizers, fragrances, surfactants, fillers, sequestering agents, anionic, cationic, non-ionic polymers or amphoteric or mixtures thereof, propellants, acidifying agents or Basifying agents, dyes, dyes, pigments or nanopigments, in particular those suitable to provide an effect additional photo-protector by physically blocking the ultraviolet radiation, or any other ingredient normally formulated in cosmetics, in particular for the production of sunscreen / sunscreen compositions. The necessary amounts of dermatological and cosmetic adjuvants and the additives, based on the desired product, can easily be chosen by an expert in this field and will be illustrated in the examples, without being limited to these.

An additional amount of Antioxidants / preservatives is generally preferred. All the known antioxidants usually formulated in cosmetics They can be used. Especially preferred are antioxidants chosen from the group consisting of amino acids (for example, the glycine, histidine, tyrosine, tryptophan) and its derivatives, imidazole (for example urocanic acid) and derivatives, peptides such as D, L-carnosine, D-carnosine, L-carnosine and derivatives (for example, anserine), carotinoids, carotenes (for example, α-carotene, β-carotene, lycopene) and derivatives, acid chlorogenic and derivatives, liponic acid and derivatives (for example, dihydroliponic acid), aurothioglucose, propylthiouracil and others thiols (e.g., thioredoxin, glutathione, cysteine, cystine, cystamine and its glycosyl-, N-acetyl-, methyl-, ethyl-, propyl-, amyl-, butyl- and lauryl-, palmitoyl-; oleiil-, γ-linoleil, cholesterol and glyceryl ether) and salts thereof, dilaurylthiopropionate, distearyl thiopropionate, and thiodiopropionic acid and its derivatives (ester, ether, peptides, lipids, nucleotides, nucleosides and salts), as well as sulfoximin compounds (such as butionine sulfoximin, homocysteine sulfoximin, butionine sulfone, penta-, hexa-, heptathione sulfoximin) in very low doses compatible (for example, pmol / kg to umol / kg), additionally (metal) - chelants (as fatty acids α-hydroxy, palmitic, phytinic acid, lactoferrin), α-hydroxy acids (such as acid citric, lactic acid, malic acid), humic acid, acid Gallic, gallic extracts, bilirubin, biliverdin, EDTA, EGTA and its derivatives, unsaturated fatty acids and its derivatives (such as, γ-linoleic acid, linolic acid, oleic acid), folic acid and its derivatives, ubiquinone and ubiquinol and its derivatives, vitamin C and derivatives (such as ascorbyl palmitate and ascorbyl tetraisopalmitate, ascorbyl phosphate Mg, phosphate ascorbil Na, ascorbil acetate), tocopherol and its derivatives (such as Vitamin E acetate, nat. vitamin E and mixtures thereof), the vitamin A and its derivatives (vitamin A acetate and palmitate), as well such as coniferylbenzoate, rutinic acid and derivatives, rutin α-glycosyl, ferulic acid, glucitol furfurylidene, butyl hydroxytoluene, butyl hydroxyanisole, trihydroxybutyrophenone, urea and its derivatives, mannose and derivatives, zinc and derivatives (for example, ZnO, ZnSO4), selenium and derivatives (for example, seleniomethionine) stilbenes and derivatives (such as stilbenexide, trans-stilbenexide) and suitable derivatives (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of the active ingredients named. One or more preservatives / antioxidants may be present in an amount from about 0.01% by weight to about 10% by weight by weight Total composition of the present invention. Preferably, one or more preservatives / antioxidants are present in a amount from about 0.1% by weight to about 1% by weight.

Examples of emulsifiers that can be used in the present invention, in order to form emulsions /
O / W, W / O, O / W / O or W / O / W microemulsions include sorbitol oleate, sorbitol sesquioleate, sorbitol isostearate, sorbitol trioleate, polyglyceryl-3-diisoesterate, polyglycerol esters of oleic / isostearic acid, polyglyceryl-6 hexaricinolate, polyglyceryl-4-oleate, polyglyceryl-4 oleate / PEG-8 propylene glycol cocoate, DEA oleamide, TEA myristate, TEA stearate, magnesium stearate, sodium stearate, potassium laurate potassium ricinoleate, sodium cocoate, sodium cebato, potassium castorate, sodium oleate, and mixtures thereof. Additional suitable emulsifiers are phosphate esters and salts thereof, such as cetyl phosphate (Amphisol® A), diethanolamine cetyl phosphate (Amphisol®), potassium cetyl phosphate (Amphisol® K), sodium glyceryl oleate phosphate, hydrogenated vegetable glyceride phosphate and mixtures thereof. On the other hand, one or more synthetic polymers can be used as an emulsifier. For example, PVP eicosenne copolymer, acrylate crospolymer / C 10-30 -alkyl acrylate, acrylate / steareth-20 methacrylate copolymer, PEG-22 / dodecyl glycol copolymer, PEG-45 / dodecyl glycol copolymer, and mixtures thereof. Preferred emulsifiers are cetyl phosphate (Amphisol® A), diethanolamine cetyl phosphate (Amphisol®), potassium cetyl phosphate (Amphisol® K), PVP eicosenne copolymer, acrylate / C 10-30 alkyl acrylate cpolymer, PEG-20 sorbitol isostearate, sorbitol isostearate, and mixtures thereof. Emulsifiers are present in a total amount of about 0.01% by weight to about 20% by weight of the total weight of the composition of the present invention. Preferably, about 0.1% by weight to about 10% by weight of emulsifier are used.

The lipid phase can be advantageously chosen from: mineral oils and mineral waxes; oils like triglycerides of caprinic acid or caprylic acid, of castor oil preference; oils or waxes and other oils natural or synthetic, in a preferred embodiment esters of fatty acids with alcohols for example isopropanol, propylene glycol, glycerin or esters of fatty alcohols with acids lower carboxylic or fatty acids; alkyl benzoates; oils silicone such as dimethylpolysiloxane, diethylpolysiloxane, diphenylpolysiloxane, cyclomethicone and mixtures thereof.

Exemplary fatty substances that can be incorporated into the oil phase of the emulsion, microemulsion, oil gel, hydrodispersion or lipodispersion of the present invention are advantageously chosen from alkyl acid esters linear or branched carboxylic acids saturated and / or unsaturated with 3 at 30 carbon atoms and linear and / or branched alcohols saturated and / or unsaturated with 3 to 30 carbon atoms, as well as esters of aromatic carboxylic acids and alcohols linear or branched saturated and / or unsaturated, of 3-30 carbon atoms. These esters can advantageously being selected from octyl palmitate, octyl cocoate, octyl isostearate, octyl dodecil myristate, cetearylisononanoate, isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyl oleate, n-butyl stearate, n-hexyl laureate, n-decyloleate, isooctyl stearate, isononyl stearate, isononyl isononanoate, 2-ethyl hexyl palmitate, 2-ethylhexyl laureate, 2-hexyldecyl stearate, 2-octyl dodecyl palmitate, stearyl heptanoate, oleyl oleate, oleilerucate, eruciloleato, tridecil stearate erucilerucato, tridecil trimellitate, and synthetic, semi-synthetic mixtures or natural of said esters for example jojoba oil.

Other fatty components suitable for use in the formulation of the present invention include oils polar such as fatty acid lecithins and triglycerides, namely Triglycerinic esters of linear or branched carbonic acid saturated and / or unsaturated, with 8 to 24 carbon atoms, preferably from 12 to 18 carbon atoms, while the fatty acid triglycerides are preferably chosen from synthetic, semi-synthetic or natural oils (for example, cocoglyceride, olive oil, sunflower oil, soybean oil, peanut oil, rapeseed oil, oil Sweet almond, palm oil, coconut oil, oil castor, hydrogenated castor oil, wheat oil, grape seed, macadamia nut oil and others); oils apolar such as linear and / or branched hydrocarbons and waxes by example mineral oils, petrolatum (petrolatum); paraffins, squalan and squalen, polyolefins, isohexadecanes and polyisobutenes hydrogenated, the favored polyolefins are polydecenes; dialquil ethers such as dicaprilyl ether; linear silicone oils or cyclic, such as preferably cyclomethicone (octamethyl cyclotetrasiloxane), cetyl dimethicone, hexamethyl cyclotrisiloxane, polydimethyl siloxane, poly (methyl phenyl siloxane) and mixtures of the same.

Still other fatty components that can be advantageously incorporated in the formulations herein invention include isoeicosan; neopentyl glycol diheptanoate; propylene glycol dicaprilate / dicaprate; diglyceryl succinate caprylic / capric; butylene glycol caprylate / caprate; C2-15 -alkyl lactates; di-C_2-15} -alkyl  tartrates; triisoestearin; dipentaerythrityl hexacaprilat / hexacaprate; propylene glycol monoisoetearate; tricaprilin; dimethyl isosorbide. Especially beneficial is the use of mixtures of C_2-15} -alkylbenzoates and 2-ethyl-hexyl isoestearate, mixtures of C_2-15} -alkylbenzoates e isotridecylisononanoate as well as mixtures of C_2-15} -alkylbenzoates, 2-ethylhexyl isoestearate e isotridecylisononanoate.

The oil phase of the formulation of the present invention may also contain animal or vegetable waxes natural as beeswax, porcelain wax, wax bumblebees and other insect waxes, as well as shea butter and cocoa butter

A moisturizing agent can be incorporated into a composition of the present invention to maintain hydration or Rehydrate the skin. The humectants that prevent water evaporates from the skin, providing a protective layer They are called emollients. Additionally, an emollient provides a soothing or softening effect on the skin's surface and is Generally considered safe for topical use. Emollients Preferred include mineral oils, lanolin, petrolatum, triglycaraldehydes, capric, capric, cholesterol, silicones, such as dimethicone, cyclomethylicone, almond oil, jojoba, avocado oil, castor oil, sesame oil, sunflower oil, coconut oil and grapeseed oil, cocoa butter, olive oil aloe extracts, acids fatty like oleic and stearic, fatty alcohols like cetil and hexadecylalcohol, diisopropyl adipate, hydroxy benzoate esters, esters of benzoic acid from C_ {15-15} -alcohols, isononyl iso-nonanoate, ethers such as polypropylene butyl ethers and polyoxypropylene cetyl esters, and C1-15-15 -alkyl benzoate, and mixtures thereof. The most preferred emollients are esters of hydroxybenzoate, aloe vera, C_2-15} -alkyl benzoates, and mixtures thereof. An emollient may be present in a amount from about 1% by weight to about 20% by weight of total weight of the composition. The preferred amount of emollient it can be from about 2% by weight to about 15% by weight, and more preferably about 4% by weight to about 10% in weight.

Moisturizers that bind to water, retaining it on the surface of the skin are called moisturizers. Suitable humectants can be incorporated into a composition of the present invention, such as glycerin, polypropylene glycol, polyethylene glycol, lactic acid, acid carboxylic pyrrolidon, urea, phospholipids, collagen, elastin, ceramides, lecithin, sorbitol, PEG-4, and mixtures of the same. Suitable additional moisturizers are moisturizers. polymers of the family of water-soluble polysaccharides and / or inflatable and / or forming a jelly with water, such as acid hyaluronic, chitosan and / or a rich fucose polysaccharide which It is, for example, available as Fucogel® 1000 (CAS-Nr. 178463-23-5) by SOLABIA S. One or more humectants are optionally present at around 0.5% by weight to about 8% by weight in a composition of the present invention, preferably about 1% by weight to about 5% in weigh.

The aqueous phase of the compositions of the The present invention may contain usual cosmetic additives, such as alcohols, especially lower alcohols, preferably ethanol and / or iso-propanol, polyols of the order of the lower diols and their ethers, preferably propylene glycols, glycerin, ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propylene glycol-mono-methyl-, monoethyl-, or monobutyl ether, diethylene glycol-monomethyl- or monoethyl ether and similar products, polymers, stabilizers foam; electrolytes and especially one or more thickeners. The suitable thickeners that can be used in the formulations of the present invention to assist in the consistency of a Product include carbomer, silicon dioxide, silicates magnesium and / or aluminum, beeswax, stearic acid, alcohol stearyl polysaccharides and their derivatives such as xanthan gum, hydroxypropyl cellulose, polyacrylamides, acrylate crospolymers preferably a carbopol, such as carbopol type 980, 981, 1382, 2984, 5984 alone or mixtures thereof. The agents suitable neutralizers that can be included in the composition of the present invention to neutralize such components such as an emulsifier or a former / stabilizer foam include but are not limited to alkali hydroxides such as potassium and sodium hydroxide; organic bases such as the diethanolamine (DEA), triethanolamine (TEA), aminomethyl propanol, and mixtures thereof; amino acids such as arginine and lysine and any combination of the above. The agent of neutralization may be present in an amount of about 0.01% by weight to about 8% by weight in the composition of the present invention, preferably, from 1% by weight to about 5% in weigh.

The addition of electrolytes in the composition of the present invention may be necessary to change the behavior of a hydrophobic emulsifier. So, the Emulsions / microemulsions of this invention may contain preferably electrolytes of one or more salts including anions such as chloride, a sulfate, a carbonate, a borate or an aluminate, without being limited to these. Other electrolytes Suitable may be based on organic anions, such as, but not limited to, lactate, acetate, benzoate, propionate, Tartrate and citrate. Like ammonia cations, preferably alkylammonium, alkali or alkali metals are selected Earth, magnesium, iron or zinc ions. The salts especially Preferred are sodium and potassium chloride, magnesium sulfate, zinc sulfate and mixtures thereof. The electrolytes are present in an amount of about 0.01% by weight to about 8% by weight in the composition of the present invention.

The cosmetic compositions of the invention are useful as compositions for the photo-protection of the human epidermis or hair against the harmful effects of the ultraviolet radiation, as a protective composition solar / anti-solar, or as a makeup product. Such compositions may, in particular, be provided in form of a lotion, a thick cream, a gel, a cream, a milk, an ointment, a powder or a solid tube shaped bar, and optionally they can be packaged in aerosol form and can be provided in the form of a cream, foam or a spray. When The cosmetic composition according to the invention is provided for the protection of the human epidermis against UV radiation or as a protective composition solar / anti-solar, can be in the form of a suspension or dispersion in solvents or fatty substances, or as alternative, in the form of an emulsion or microemulsion (in particular, of type O / W or W / O, of type O / W / O or W / O / W), as a cream or a milk, a vesicular dispersion, in the form of an ointment, a gel, a solid tube shaped bar or a spray cream. Emulsions may also contain anionic surfactants, not ionic, cationic or amphoteric.

When the cosmetic composition according to The invention is used to protect the hair, it can be in shape of a shampoo, lotion, gel or rinse composition, to be applied before or after shampoo, before or after dye or discoloration, before, during or after the operation of hair straightening or perm, a lotion or treatment gel or stylist, a lotion or a gel for drying by air or hair arrangement, a hairspray, or a Composition for perm, straightening, dyeing or hair discoloration

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When the cosmetic composition according to The invention is used as a makeup product for eyelashes, eyebrows, skin or hair, as a treatment cream epidermal, a base, a tube of lipstick, an eye shadow, a face powder, an eyeliner, a mask or a gel color, this can be solid or pasty, anhydrous or in aqueous form, as an O / W or W / O emulsion, suspension or gel.

The present invention also includes the formulation of organosilicon compounds according to the invention as an agent for the protection of UV radiation, in particular, to control the color of human skin.

The organosilicon compounds according to the present invention show excellent fat solubility and therefore they can be incorporated in high concentrations in the cosmetic formulations that lead to a protective factor elevated of the final compositions. In addition, they are homogeneously distributed in the cosmetic formulation containing at least one phase of fat and a cosmetically organic solvent accepted that leads, when applied to the skin or hair, to the formation of a protective film that effectively protects the skin and / or hair against the harmful effects of radiation UV

Thus, it is another object of the present invention the use of the compounds of the invention to protect the skin and / or the ultraviolet radiation hair in particular radiation solar, which includes the topical application of an effective amount of a cosmetic composition containing the compounds organosilicon according to the invention.

Finally, the present invention also characterizes the non-therapeutic regimen / control regime of the variation of skin color caused by radiation ultraviolet, which includes topical application on the skin of a effective amount of a cosmetic composition containing the organosilicon compounds according to the invention.

According to another embodiment of the invention, An organosilicon compound of this invention can be used as UV protective agent for plastics.

The organosilicon derivatives of the invention They are also photo-stable.

In accordance with the foregoing, the invention provides

(1) An organosilicon compound for use as a UVA filter, for example, for use in a composition cosmetic

(2) A cosmetic composition comprising a organosilicon compound as in (1) as active ingredient, together with cosmetically accepted adjuvants and additives, in particular, a composition further comprising a protective agent selected from the group formed by protection agents UV-A rays, protective agents against UV-B rays, and mixtures thereof, by example, a complementary UV protection agent inorganic, as a pigment or nanopigment with or without coating of a metal oxide selected from the oxides of titanium, zinc, iron, zirconium and cerium;

(3) A cosmetic composition comprising a organosilicon compound as in (1) as active ingredient together with cosmetically accepted adjuvants and additives for protection of human hair and / or skin against damage to that UVA irradiation plays a role or is involved;

(4) A method for hair protection human and / or skin against damage in which UVA irradiation plays a role or that is implied that understands the application topical of an effective amount of an organosilicon compound as in 1);

(5) Use of an organosilicon compound as in (1) to protect human hair and / or skin against damage to those that UVA irradiation plays a role or is involved.

The following examples are provided for better illustrate the processes and compositions of this invention. These examples are illustrative only and are not intended to limit the scope of the invention in any way. In the examples, FC means Flash chromatography; HV means high vacuum (0.1 Pa or below); INCI means Nomenclature International Cosmetic Ingredients. All structures were clearly identified through 1 H-NMR (300 MHz, CDCl3). The Photo-stability of the products was measured from agreement to Berset and others; Internat. J. Cosmetic Science 18: 167-177 (1996).

Example A1

Preparation of prop-2-inyl ester of the acid 2- (4-diethylamino-2-hydroxybenzoyl) benzoic

A mixture of 32 mmol of the acid 2- (4-diethylamino-2-hydroxybenzoyl) benzoic, 160 mmol of propargyl alcohol and 32 mmol H 2 SO 4 is refluxed for 48 hours. After the evaporation of excess propargyl alcohol, the residue is Dissolve in ethyl acetate and then wash twice with a saturated solution of NaHCO3 and twice with water. After from drying (Na2SO4), the solvent evaporates (HV) and the raw product is purified twice through FC (n-hexane / EtOAC 1: 1, hexane / MTBE 4 / 1-1 / 1) producing prop-2-inyl acid ester 2- (4-diethylamino-2-hydroxybenzoyl) benzoic. MS (EI): 374 (18%, M + Na +), 352 (100%, M + H +), 296 (17%). UV (EtOH): λ max = 356 nm (? = 31'648).

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Example A2

Preparation of allyl acid ester 2- (4-diethylamino-2-hydroxybenzoyl) benzoic

A mixture of 32 mmol of the acid 2- (4-diethylamino-2-hydroxybenzoyl) benzoic, 160 mmol of allyl alcohol and 32 mmol of H 2 SO 4 It is refluxed for 48 h. After evaporation of excess allyl alcohol the residue is dissolved in ethyl acetate and, subsequently washed twice with a saturated solution of NaHCO 3 and twice with water. After drying (NaSO4), The solvent is evaporated (HV) and the crude product is purified to through FC (n-hexane / EtOAC 2: 1, hexane) producing allyl acid ester 2- (4-diethylamino-2-hydroxybenzoyl)  benzoic. MS (EI): 376 (10%, M + Na +), 354 (100%, M + H +), 296 (17%). UV (EtOH): λ max = 354 nm (? = 34'257).

Example A3

Preparation of 2- (4-diethylamino-2-hydroxybenzoyl) -benzamide propargilic

A mixture of 6 g of the acid 2- (4-diethylamino-2-hydroxybenzoyl) Benzoic and 1.6 g of propargyl amine is dissolved in 20 ml of DMF with cooling to form a clear solution. 5.9 g of Dicyclohexyl carbodiimide is added slowly to this solution. The mixture is diluted with 20 ml of CH2C2 and left to room temperature for two hours. The suspension formed is Filter and wash with hexane and ether. The organic phase is diluted with EtOAc, washed with saturated NaHCO3 solution, three times with water and once with saturated NaCl solution. After drying (Na 2 SO 4), the solvent is evaporated (HV) and the product purified crude via FC (n-hexane / EtOAC 2: 1, hexane) and recrystallized from a mixture of hexane, toluene and EtOAc, producing white crystals of 2- (4-diethylamino-2-hydroxybenzoyl) -benzamide propargilic MS: 351 (M + H +), 333.296 (100%).

Example B1

Preparation of a compound in which B, B ', R 1, R 6, R 7, R 8, R 9, R 10 and R 11 are methyl, Z is a group of the formula III where R 3 and R 4 are ethyl and -X-Y- is -O-CH 2 -C (CH 2) - (main isomer), r is in its statistical mean 14 and s is in its statistical average 4

A solution of 1.75 mmol of prop-2-inyl acid ester 2- (4-diethylamino-2-hydroxybenzoyl) benzoic and 1.75 mmol eq. SiH of a COMPOUND in which B, B ', R 1 and R 2 are methyl, Z is H, r is in its statistical average 14 and s is in its statistical average 4 (MW-1500) in 3 ml of toluene under an inert atmosphere is heated to 55 ° C. A Catalytic amount of 5% carbon platinum is added and the reaction it is maintained at 55 ° C for 20 h. The product solution is washed with a mixture of water / methanol = 1:10, it is dried (Na2SO4), and It concentrates. After the residue is dissolved in 3 ml of toluene, active carbon is added and the mixture is stirred for 2 d at TA After filtration on Celite, the solvent is evaporated to produce a yellow oil (two isomers). UV (EtOH): 354 nm (E = 477), having unlimited solubility in Cetiol LC and Crodamol DA and photo-stability qualities Excellent in the movie.

Example B2

Preparation of a COMPOUND in which B, B ', R 1 R 6, R 7, R 8, R 9, R 10 and R 11 are methyl, Z is a group of the formula III where R 3 and R 4 are ethyl and -X-Y- is -O-CH 2 -C (CH 2) - (main isomer), r is in its statistical average 60 and s is in its statistical average 4

0.5 g of prop-2-inyl acid ester 2- (4-diethylamino-2-hydroxybenzoyl) benzoic, 2 g of polysiloxane AE-151 from Wacker-Chemie GmbH, and a catalytic amount of 5% carbon platinum in 10 ml of xylene are placed in a bottle of three-necked reaction under an inert atmosphere and heats up for 2 h at 70 ° C. The product solution is filtered through Celite, washed with a mixture of water / methanol = 1:10 and concentrated to produce a brown oil (two isomers). UV 354 nm (E = 147), having unlimited solubility in Cétiol LC and Crodamol DA and excellent photo-stability qualities in the movie.

Example B3

Preparation of a COMPOUND in which B, B ', R 1, R 6, R 7, R 8, R 9, R 10 and R 11 are methyl, Z is a group of the formula III where R 3 and R 4 are ethyl and -X-Y- is -NH-CH 2 -C (CH 2) - (main isomer), r is 0 and s is 1

A solution of 1.4 mmol of 2- (4-diethylamino-2-hydroxybenzoyl) -benzamide propargyl and 1.2 mmol of heptamethyltrisiloxane of formula IV where B, B ', R 1 and R 2 are methyl, Z is hydrogen, r is 0 and s is 1, in 10 ml of toluene under an inert atmosphere is heated to 55 ° C. An amount of the complex platinum-divinyl-tetramethyl-disiloxane  it is added and the reaction is maintained at 80 to 85 ° C for 36 hours and at 100 ° C for four hours. 0.3 g heptamethyltrisiloxane Additional and a small amount of catalyst are added. After heating for another 18 hours at reflux, the solution of the product is concentrated and chromatographed twice (CH 2 Cl 2 / MeOH) to produce the product (two isomers). UV (EtOH): 358 nm (E = 227).

Example C1 Preparation of a broad spectrum sunscreen lotion containing 2% of an organosilicon compound of the invention

9

Part A is heated in a reactor at 85 ° C. The Part B is added slowly within 10 minutes, followed by the addition of KOH, cooling and degassing of the emulsion.

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Example C2

Preparation of a broad spectrum sunscreen lotion containing 4% of an organosilicon compound of the invention

eleven

Part A is heated in a reactor at 85 ° C. The Homogeneous Part B is added, followed by the addition of KOH preheated (75ºC), cooling and degassing of the emulsion.

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Example C3

Preparation of a broad spectrum sunscreen cream containing 4% of a polysiloxane compound of the invention

13

Part A is heated to 85 ° C while stirring and then mix for 30 seconds with a turbine at 8000 rev / minute When it is homogeneous, Part B is pre-heated to 75 ° C and added to Part A.

The mixture is cooled to 40 ° C and Part C is Add. Water loss is compensated and stirring is continued during cooling to room temperature. Then the mixture is mixed for 30 seconds with a turbine at 8000 rev / minute.

The cream has a low quality of skin penetration

Claims (7)

1. An organosilistic compound comprising a unit of formula I 14 where a is 0, 1 or 2, R1 is hydrogen, a hydrocarbon group C_ {1} -C_ {30} saturated or unsaturated or a group trimethylsilyloxy; Y Z is an amino substituted hydroxybenzophenone of formula III fifteen where R 3 and R 4 are independently hydrogen, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 3 -C 10 cycloalkyl or C 3 -C 10 cycloalkenyl or R 3 and R 4, together with the nitrogen atom to which they are attached, they form a 5 to 6 member ring; X is -O- or -NR 5 - where R 5 is hydrogen, C 1 -C 20 alkyl, C 2 -C 2 Oalquenil, C 3 -C 10 cycloalkyl or C 3 -C 10 cycloalkenyl; Y And it is an alkenylene chain or C 3 -C 12 divalent alkylene; and, optionally, a unit of the formula II 16 where b is 0, 1, 2, 3; Y R2 is hydrogen, a hydrocarbon group C_ {1} -C_ {30} saturated or unsaturated or a group trimethylsilyloxy.

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2. A diorgano-siloxane polymer linear comprising a structural unit of the formula IVa and a structural unit of formula IVb 17

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s units of the formula IVc 18 And r units of the formula IVd 19 where Z is as defined in the claim one; R 1, R 6, R 7, R 8, R 9, R 10 and R 11 independent are as defined in the claim 1 for R2; B and B 'independently are a group Z or a R2 group; r is an integer from 0 to 200; Y s is an integer from 0 to 50, in which, at least B or B 'is Z when s is 0.

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3. A process for the preparation of a organosilicon compound according to claim 1 which comprises reacting (hydrosilylation) an organosilicon compound comprising a unit of formula VI twenty where a is 0, 1 or 2; Y R1 is hydrogen, a hydrocarbon group C_ {1} -C_ {30} saturated or unsaturated or a group trimethylsilyloxy; And, optionally, a unit of formula II of according to claim 1, with a compound of formula VII twenty-one in which R 3, R 4, and X are as defined in claim 1 and Y 'has the same definition that Y in claim 1, but ends with a double or a triple link.

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4. A cosmetic composition comprising a organosilicon compound as in claim 1 together with Cosmetically accepted additives and adjuvants.

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5. A cosmetic composition comprising a organosilicon compound as in claim 1 for the protection of human hair / or skin against damage in which the UVA irradiation plays a role or is involved. 6. A method for hair protection human / or skin against damage in which UVA irradiation plays a role or is involved that includes applying so topical an effective amount of an organosilicon compound such as the of claim 1. 7. Use of an organosilicon compound such as claim 1 for the protection of human hair / or skin against damage in which UVA irradiation plays a role or It is involved.